ELLIPSOMETRY AS A PROBE OF THIN COPOLYMER FILMS: CRYSTALLISATION & MORPHLOGY

Abstract

This study presents results on the use of ellipsometry as a novel probe for thin films of a diblock copolymer. Ellipsometry makes use of the change in polarisation induced upon reflection of light from a film covered substrate to enable calculation of the refractive index and thickness of the film. The infom1ation obtained in these measurements can be compared to differential scanning calorimetry, with the additional advantages that small sample volumes and slow cooling rates can be employed, and expansion coefficients can be determined. The work is presented in two parts; first crystallisation within the phase-separated domains is studied, then a morphological transition in the diblock ordering is characterised. By studying the temperature dependence of the film thickness and refractive index, crystallisation kinetics within very small volumes( 10^-10 L) of a poly (butadiene-b-ethylene oxide) diblock copolymer are measured. Through a comparison of two different PEO block lengths, a reduction in both the crystallisation and melting temperatures is demonstrated as the domain volume is decreased. Upon cooling, an additional transition is observed. We ascribe this to a morphological transition from a layer of ordered spheres to a lamellar layer at the substrate, which is consistent with a comparison between the data and simulated ellipsometry data. The sensitivity of ellipsometry makes it a well suited and versatile technique for probing thin film kinetics in diblock copolymers.